Nanomaterials Processing of Dyes and Organic Compounds

Abstract

Provided is a method comprising contacting a composition comprising metal oxide nanofilaments with a sample comprising a dye and / or an organic compound under conditions such that the dye and / or organic compound associate with the composition, and wherein the metal oxide nanofilaments optionally comprise titanium, the metal oxide nanofilaments optionally comprise carbon, and the oxide nanofilaments optionally have a lepidocrocite structure. Also provided is a system comprising a conduit and an amount of a composition comprising metal oxide nanofilaments, the conduit fluidly connecting the composition with a process stream, the process stream comprising the dye and / or the organic compound.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Patent Application No. 63 / 309,411, entitled "Nanomaterial-Based Processing Of Dyes And Organic Compounds," filed February 11, 2022. All of the foregoing applications are hereby incorporated by reference in their entireties for all purposes.

[0002] The present disclosure relates to the field of one-dimensional nanomaterials. [Background technology]

[0003] Certain dyes and organic compounds may be undesirable as they may cause health effects in people who come into contact with them and pose other environmental risks. Thus, there is a long felt need for a method to degrade the dyes and / or organic compounds. Summary of the Invention

[0004] To meet the stated long-standing needs, the present disclosure provides a method comprising: contacting a composition comprising metal oxide nanofilaments with a dye and / or an organic compound under conditions such that the dye and / or organic compound undergo at least partial decomposition or decomposition, wherein the metal oxide nanofilaments optionally comprise titanium, the metal oxide nanofilaments optionally have a one-dimensional anatase structure, and optionally comprise carbon, and the structure of the oxide nanofilaments optionally is a lepidocrocite structure, or a one-dimensional lepidocrocite (1DL) structure, and further optionally illuminating the composition and the dye and / or organic compound.

[0005] Also provided is a system, the system comprising a conduit and an amount of a composition comprising metal oxide nanofilaments, the metal oxide nanofilaments optionally comprising titanium, the metal oxide nanofilaments optionally comprising carbon, and the structure of the oxide nanofilaments optionally being a lepidocrocite structure, the conduit fluidly connecting the composition to a process stream, the process stream comprising a dye and / or an organic compound. [Brief description of the drawings]

[0006] In the drawings, which are not necessarily drawn to scale, like numbers may represent like components in different views. Like numbers with different letter suffixes may represent different instances of the like components. The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed in the present specification.

[0007] [Figure 1] FIG. 1 provides exemplary wavelength vs. absorbance data for an aqueous solution of 1DL and Rhodamine 6G, as well as exemplary time vs. dye remaining data for said aqueous solutions of 1DL and Rhodamine 6G (left panel). [Diagram 2] FIG. 2 is a calibration curve for an aqueous solution of rhodamine 6G. [Diagram 3] FIG. 3 shows exemplary data for planktonic populations of 1DL and rhodamine 6G in water before (left panel) and after (right panel) illumination. [Figure 4] FIG. 4 qualitatively illustrates the decolorization of rhodamine 6G in aqueous 1DL solution before (right panel) and after (left panel) filtration. [Diagram 5] Figure 5 provides wavelength vs. absorbance data for an aqueous solution of 1DL and rhodamine 6G at various times of exposure and filtered to remove all 1DL. This exemplary wavelength vs. absorbance data corresponds to the solution in Figure 4, right panel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present disclosure may be understood more readily by reference to the following detailed description of the preferred embodiments and the examples included therein.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the present specification, including definitions, shall prevail. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein may be used in the practice or testing. All publications, patent applications, patents and other documents described herein are incorporated by reference in their entirety. The materials, methods and examples disclosed herein are illustrative only and are not intended to be limiting.

[0010] The singular forms "a," "an," and "the" include plural referents unless the context clearly indicates otherwise.

[0011] As used herein and in the claims, the term "comprising" may include the embodiments "consisting of" and "consisting essentially of." As used herein, the terms "comprise(s), "include(s), "having(s), "has(s), "can(s), "contain(s)," and variations thereof, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named components / steps and permit the presence of other components / steps. However, such descriptions should also be construed as describing compositions or steps as "consisting of" and "consisting essentially of" the listed components / steps, which permits only the named components / steps to be present along with impurities that may result therefrom, and excludes other components / steps.

[0012] As used herein, the terms "about" and "at or about" mean that the quantity or value in question may be approximately or approximately the same as the other value specified. As used herein, it is generally understood to be a variation of ±10% of the nominal value unless otherwise indicated or inferred. The term is intended to convey that similar values ​​promote the same results or effects as described in the claims. That is, it is understood that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not and do not have to be exact, but can be approximated and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. In general, the amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate", whether or not they are expressly stated as such. When "about" is used before a quantitative value, it is understood that the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0013] Unless otherwise indicated to the contrary, numerical values ​​should be understood to include numerical values ​​that are the same when reduced to the same significant figures, and numerical values ​​that differ from the stated value by less than experimental error using conventional measuring techniques of the type described herein to determine the numerical value.

[0014] All ranges disclosed herein are inclusive of the recited endpoints and are independent of the endpoints (e.g., "between 2 grams and 10 grams, and all intermediate values, including 2 grams, 10 grams, and all intermediate values"). The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, but are sufficiently imprecise to include values ​​that are close to these ranges and / or values. All ranges are combinable.

[0015] As used herein, approximation may be applied to modify any quantitative expression that may vary without resulting in a change in the basic function to which it is related. Thus, a value modified by terms such as "about" or "substantially" may in some cases not be limited to the exact value specified. At least in some cases, an approximation may correspond to the precision of an instrument for measuring the value. The modifier "about" should also be considered to disclose a range defined by the absolute values ​​of the two endpoints. For example, the phrase "from about 2 to about 4" also discloses the range "from 2 to 4". The term "about" may refer to plus or minus 10% of the indicated numerical value. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may mean 0.9 to 1.1. Other meanings of "about" may be clear from the context, such as rounding, so for example, "about 1" may mean 0.5 to 1.4. Additionally, the term "comprising" should be understood to have the open-ended meaning of the term "including," but also includes the closed meaning of the term "consisting." For example, a composition consisting of components A and B may be a composition containing A, B, and other components, but may also be a composition consisting only of A and B. All documents cited herein are incorporated by reference in their entirety for all purposes.

[0016] Working Example The following examples are illustrative, and do not limit the scope of the disclosure or the appended claims.

[0017] Exemplary embodiments The following exemplary embodiments are illustrative only and are not limiting of the scope of the disclosure or the appended claims. EXAMPLES

[0018] Example 1-1 Synthesis of DL 10 g of binary titanium precursor (e.g., TiB2, TiN, TiC) powder was mixed with 100 mL of aqueous tetramethylammonium hydroxide (25 w / w) at 80 °C for 72 h. The resulting supernatant was washed with ethanol until it was neutral. The neutral material was suspended in water to obtain a stable colloidal suspension. EXAMPLES

[0019] Example 2 - Contact-adsorption regime of 1DL on rhodamine 6G 0.4 mL of 1 g / L colloidal 1DL is added to 38.8 mL of deionized water and mixed for 1 minute to allow binding. 0.8 mL of the 500 mg / L dye solution is then added to the 1DL aqueous solution. 1DL - dye aggregates - or flocs - formed within 5 minutes of stirring at 400 RPM, as shown in Figure 5. The flocs can be removed from the solution with a 0.45 um PTFE syringe filter, and the overall kinetics of dye removal can be monitored with an ultraviolet-visible (UV Vis) light (Figure 1-dark) spectrometer utilizing a calibration curve (Figure 2). EXAMPLES

[0020] Example 3 - Contact-adsorption regime of 1DL on rhodamine 6G 4 mL of 1 g / L colloidal 1DL is added to 35.2 mL of deionized water and mixed for 1 minute to allow binding. Then, 0.8 mL of the 500 mg / L dye solution is added to the aqueous 1DL. With stirring at 400 RPM, a 1DL-dye complex is immediately formed as shown in Figure 6. This complex can be removed from the solution by filtration through a Celgard ion exchange membrane and removal can be monitored by UV-Vis (Figure 1 - dark) utilizing a calibration curve (Figure 2). EXAMPLES

[0021] Example 4-1 Catalysis of DL and Rhodamine 6G - Decomposition under solar spectrum After the adsorption zone, a xenon lamp (solar simulator) or sunlight can be applied to the solution system. Significant decolorization is observed even without removing an aliquot. The rate of decolorization is proportional to the ratio of 1DL to rhodamine 6G and the power of the light source. Figures 1 (inset) and 4 show the decolorization as a function of irradiation time.

[0022] Aspects The following aspects are illustrative and not limiting of the scope of the disclosure or the appended claims. Any part or portion of any one or more aspects may be combined with any part or portion of any one or more other aspects.

[0023] Embodiment 1. A method comprising contacting a composition comprising metal oxide nanofilaments with a sample comprising a dye and / or an organic compound under conditions such that the dye and / or the organic compound associate with the composition, and wherein said metal oxide nanofilaments optionally comprise titanium, said metal oxide nanofilaments optionally comprise carbon, and said oxide nanofilaments optionally have a lepidocrocite structure.

[0024] The metal oxide nanofilaments can optionally have a titanium oxide lepidocrocite structure. The metal oxide nanofilaments can optionally be one-dimensional nanofilaments (which can be lepidocrocite) with a cross section of 1 nm or less.

[0025] The association between the dye and / or organic compound and the metal oxide nanofilaments can be an adsorption.

[0026] Titanium oxide nanofilaments are believed to be particularly suitable. Examples of one-dimensional nanofilaments are described in Badr et al., "Bottom-Up, Scalable Synthesis Of Anatase Nanofilament-Based Two-Dimensional Titanium Carbo-Oxide Flakes", Materials Today 2021 (https: / / doi.org / 10.1016 / j.mattod.2021.10.033) and Badret et al., "On the structure of one-dimensional TiO2 lepidocrocite", Matter 2023 (https: / / doi.org / 10.1016 / j.matt.2022.10.015). It should be understood that the nanofilaments can be in the form of mesoporous material (e.g., powder), in the form of sheets, and in other forms. It should be understood that the nanofilaments can be tubular.

[0027] The composition and the dye and / or organic compound can be present in a solvent, such as water. Other solvents (polar solvents, non-polar solvents, alcohols, etc.) can also be used. The contact can be performed at about 20 to about 95°C, or about 25 to about 75°C, or about 30 to about 70°C, or about 35 to about 65°C, or about 40 to about 60°C, or about 45 to about 55°C, or even about 50°C. The contact can be, for example, about 5 minutes to about 5 hours, about 10 minutes to about 4.5 hours, about 15 minutes to about 4 hours, about 20 minutes to about 3.5 hours, about 30 minutes to about 3 hours, about 45 minutes to about 2 hours, or any combination or range thereof.

[0028] Aspect 2. The method of claim 1, further comprising the step of causing at least partial decomposition or decomposition of the dye and / or the organic compound, and optionally further comprising the step of irradiating the composition and the dye and / or the organic compound with light. Without being bound to a particular theory or embodiment, illumination can cause at least partial decomposition or decomposition of the dye and / or the organic compound.

[0029] Aspect 3. The method of claim 2, wherein the irradiating comprises xenon lamp illumination. Other forms of illumination may also be used, such as natural light, or UV light.

[0030] Aspect 4. The method of any one of claims 2-3, wherein the at least partial decomposition produces one or more fragments. In one embodiment, the fragments may be fragments of a dye and / or an organic compound.

[0031] Embodiment 5. The method of any one of claims 1 to 3, wherein the dye comprises any one or more of rhodamine 6G, methylene blue, methyl orange, and crystal violet. Other suitable dyes include, for example, Alcian Blue 8GX, Alcian Yellow GXS, Alizarin, Alizarin Red S, Alizarin Yellow GG, Alizarin Yellow R, Azophloxine, Bismarck Brown R, Bismarck Brown Y, Phenylene Brown, Brilliant Cresyl Blue, Chrysoidine R, Chrysoidine Y, Congo Red, Crystal Violet, Ethyl Green, Fuchsin Acid, Gentian Violet, Janus Green, Lissamine Fast Yellow, Malachite Green, Martius Yellow, Meldola Blue, Metanil Yellow, Methyl Orange, Methyl Red, Methylene Blue, Naphthalene Black, Naphthol Green B, Naphthol Yellow S, Orange G, Purpurin, Rose Bengal, Sudan II, Titan Yellow, Tropaeolin O, Tropaeolin OO, Victoria Blue 4R, Victoria Blue B, Victoria Blue R, Xylene Cyanol FF, or combinations thereof.

[0032] Aspect 6. The method of any one of claims 1-5, wherein the organic compound comprises any one or more of benzene, phenol, phthalate ester, methine, azo, phthalocyanine, triarylmethane, and amino and / or nitro groups.

[0033] Embodiment 7. The method of any one of claims 1 to 6, wherein the contacting step is carried out in a recycle manner.

[0034] Embodiment 8. The method according to any one of claims 1 to 7, wherein the contacting step is carried out in a single pass.

[0035] Aspect 9. The method of any one of claims 1 to 8, further comprising the step of determining the level of said dye and / or said organic compound in said sample prior to contacting said sample with a composition comprising said metal oxide nanofilaments.

[0036] Aspect 10. The method of any one of claims 1 to 9, further comprising the step of determining the level of said dye and / or said organic compound in said sample after contacting said sample with a composition comprising said metal oxide nanofilaments.

[0037] Embodiment 11. The method of claim 9, further comprising providing additional contact between the sample and a composition comprising the metal oxide nanofilaments if the level is equal to or greater than a threshold level.

[0038] Aspect 12. The method of claim 11, wherein the level is determined spectroscopically.

[0039] Aspect 13. The method of claim 12, wherein the level is determined by comparing absorbance at a wavelength to a standard.

[0040] Aspect 14. The method of claim 13, wherein the level is determined by comparing an absorbance at a first wavelength to an absorbance at a second wavelength.

[0041] Aspect 15. The method of any one of claims 2 to 14, further comprising the step of collecting the products of at least partial decomposition. The collecting step can be, for example, by filtration or centrifugation.

[0042] A system comprising a conduit and a quantity of a composition comprising metal oxide nanofilaments, the conduit fluidly connecting the composition to a process stream, the process stream comprising a dye and / or an organic compound. The system may be configured such that the dye and / or organic compound associate with, e.g., adsorb to, the metal oxide nanofilaments.

[0043] Suitable metal oxide nanofilaments are described elsewhere herein.The composition comprising the metal oxide nanofilaments can be, for example, an aqueous solution.

[0044] As one example, a cartridge of metal oxide nanofilaments can be positioned such that a stream of effluent from a chemical process plant passes through the metal oxide nanofilaments, thereby providing the metal oxide nanofilaments with an opportunity to adsorb / decompose dyes and / or organic compounds that may be contained in the effluent. The system can also include an illumination source (e.g., a xenon lamp, UV light), and without being bound to a particular theory, the illumination can result in improved decomposition performance by the metal oxide nanofilaments.

[0045] Aspect 17. The system of claim 16, wherein the system operates in a continuous manner.

[0046] Aspect 18. The system of claim 16, which operates in a batch or semi-batch mode.

[0047] As an example, an aqueous colloidal suspension of metal oxide nanofilaments can be added to a process stream (e.g., a waste stream) to give the metal oxide nanofilaments an opportunity to adsorb dyes and / or organic compounds that may be present in the process stream. The adsorbed material can be separated by centrifugation or filtration, or by settling the adsorbed / deagglomerated material. The system can also include an illumination source (e.g., a xenon lamp); without being bound to a particular theory, the illumination can break down the adsorbed dyes and / or organic compounds from the metal oxide nanofilaments, allowing for re-addition, reuse, and / or recycling of the nanofilaments to the process stream where the nanofilaments can adsorb additional dyes and / or organic compounds. In this way, the nanofilaments adsorb the dye, the dye is broken down into components, and then the "clean" nanofilaments are reintroduced into the process stream to adsorb other dyes in the process stream. Without being bound to a particular theory or embodiment, the aforementioned method can be repeated such that a given dye is broken down into CO2 and / or water and / or nitrogen and / or nitrates.

[0048] As an example, the disclosed method can include: (a) adsorbing dye molecules to the nanostructures; (b) under illumination, the dye breaks down into fragments, and the dye molecule fragments can be detached from the nanostructures; (c) the detached dye fragments re-adsorb onto the nanostructures; (d) under illumination, sub-fragments of the dye detach from the nanostructures; and (e) repeating steps c and d until the dye is CO2 and / or water and / or nitrogen and / or nitrates.

Claims

1. 1. A method comprising: contacting a composition comprising metal oxide nanofilaments with a sample comprising a dye and / or an organic compound under conditions such that the dye and / or the organic compound become associated with the composition; and the metal oxide nanofilaments optionally comprise titanium; the metal oxide nanofilaments optionally comprise carbon; The method, wherein said oxide nanofilaments optionally have a lepidocrocite structure.

2. 2. The method of claim 1, further comprising the step of causing at least partial decomposition or decomposition of the dye and / or the organic compound, and optionally further comprising the step of irradiating the composition and the dye and / or the organic compound with light.

3. The method of claim 2 , wherein the illumination comprises xenon lamp illumination.

4. The method of any one of claims 2 to 3, wherein the at least partial degradation produces one or more fragments.

5. The method of any one of claims 1 to 3, wherein the dye comprises any one or more of rhodamine 6G, methylene blue, methyl orange, and crystal violet.

6. The method of any one of claims 1 to 3, wherein the organic compound comprises any one or more of benzene, phenol, phthalate ester, methine, azo, phthalocyanine, triarylmethane, and amino and / or nitro groups.

7. The method of any one of claims 1 to 3, wherein the contacting step is carried out in a recycle manner.

8. The method of any one of claims 1 to 3, wherein the contacting step is performed in a single pass.

9. The method of any one of claims 1 to 3, further comprising the step of determining the level of said dye and / or said organic compound in said sample prior to contacting said sample with a composition comprising said metal oxide nanofilaments.

10. The method of any one of claims 1 to 3, further comprising the step of determining the level of said dye and / or said organic compound in said sample after contacting said sample with a composition comprising said metal oxide nanofilaments.

11. 10. The method of claim 9, further comprising providing further contact between the sample and a composition comprising the metal oxide nanofilaments if the level is equal to or greater than a threshold level.

12. The method of claim 11 , wherein the level is determined spectroscopically.

13. 13. The method of claim 12, wherein the level is determined by comparing absorbance at a wavelength to a standard.

14. 14. The method of claim 13, wherein the level is determined by comparing an absorbance at a first wavelength to an absorbance at a second wavelength.

15. The method of any one of claims 2 to 3, further comprising the step of collecting the products of at least the partial decomposition.

16. 1. A system comprising: a conduit; and a quantity of a composition comprising metal oxide nanofilaments, the conduit fluidly connecting the composition to a process stream, the process stream comprising a dye and / or an organic compound.

17. 17. The system of claim 16, wherein the system operates in a continuous manner.

18. 17. The system of claim 16, wherein the system operates in a batch or semi-batch mode.

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